US4555580A - Process for the preparation of thioindigo compounds - Google Patents

Process for the preparation of thioindigo compounds Download PDF

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US4555580A
US4555580A US06/535,543 US53554383A US4555580A US 4555580 A US4555580 A US 4555580A US 53554383 A US53554383 A US 53554383A US 4555580 A US4555580 A US 4555580A
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acid
halide
process according
chloride
inorganic acid
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Detlef-Ingo Schutze
Reinold Schmitz
Klaus Wunderlich
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Bayer AG
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Bayer AG
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B7/00—Indigoid dyes
    • C09B7/10—Bis-thionapthene indigos

Definitions

  • the invention relates to an improved process for the preparation of thioindigo compounds by reacting arylthioglycolic acids in a reaction mixture consisting of chlorosulphonic acid and a halide of an inorganic acid, such as, for example, thionyl chloride, sulphuryl chloride, phosphorus oxychloride, phosphorus(V) chloride, phosphorus(III) chloride, disulphur dichloride or the like, at temperatures between -10° C. and +35° C.
  • the resulting reaction product is then, if appropriate, oxidised in a manner which is in itself known.
  • German Patent Specification No. 243,087 discloses a process in which arylthioglycolic acids are reacted in chlorosulphonic acid. To complete the reaction to give thioindigo compounds, for example nitrobenzene is added.
  • thioindigo and its derivatives are obtained in very high yields and in a high degree of purity if arylthioglycolic acids are reacted in a mixture of chlorosulphonic acid and a halide of an inorganic acid, preferably a halide of a sulphur- or phosphorus-containing inorganic acid, for example thionyl chloride, sulphuryl chloride, phosphorus oxychloride, phosphorus(V) chloride, phosphorus(III) chloride, disulphur dichloride or the like.
  • Thioindigo compounds which can be obtained according to the invention can be represented by the formula ##STR3## in which A and B designate identical or different, optionally substituted benzene rings or benzene rings to which further carbocyclic or heterocyclic rings are fused.
  • a and B have the abovementioned meaning and which are reacted in a mixture of chlorosulphonic acid and a further halide of an inorganic acid.
  • the process is particularly suitable for the preparation of compounds of the formula (I), in which A and B designate benzene rings which are unsubstituted or carry 1, 2, 3 or 4 substituents from the series comprising halogen, nitro, trifluoromethyl, alkyl, alkoxy, aryloxy, acylamino, alkylmercapto or --COR, in which R represents alkyl, aryl, alkoxy or optionally substituted amino, or also for the preparation of compounds of the formula (I) in which a carbocyclic or heterocyclic-aromatic ring is fused to rings A and B, which may be carrying 1 to 2 substituents.
  • rings A and B carry 1, 2, 3 or 4 substituents from the series comprising chlorine, bromine, nitro or C 1 -C 4 -alkoxy or in which benzene rings A and B are part of an ⁇ - or a ⁇ -naphthyl ring.
  • the amounts and the mixing ratios of chlorosulphonic acid and the halide of an inorganic acid can vary within wide ranges.
  • arylthioglycolic acid per 1 mol of arylthioglycolic acid, 5-30 mols of chlorosulphonic acid, preferably 10-25 mols, and 0.5-3 mols, preferably 1-2.5 mols, of the acid halide to be used are employed.
  • the reaction temperature is within the range from about -10° C. to about +35° C., preferably within the range from about 0° C. to about +10° C.
  • the process is carried out by adding at an indicated reaction temperature an arylthioglycolic acid to a mixture of chlorosulphonic acid and an acid halide.
  • Times for the reaction are then chosen depending on the type of arylthioglycolic acid and are between 2 and 20 hours.
  • the reaction mixture is then discharged onto ice water, filtered off with suction and washed with water.
  • the water-moist isolated product depending on the reaction conditions used, can then consist of
  • the product obtained can be used directly as a vat dyestuff or pigment after it has been isolated and dried.
  • the product also contains a 3-hydroxy-1-thionaphthene (case 2 and 3)
  • bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia or barium hydroxide, and oxidased.
  • This is preferably carried out at a pH between 9 and 14.
  • the oxidation can be carried out here with oxygen, oxygen-containing gases, for example air, potassium dichromate, sodium polysulphide, iron(III) salt complexes, ammonium peroxodisulphate, potassium permanganate or other oxidising agents.
  • the oxidation can also be carried out in an aqueous organic phase, such as water/pyridine, water/ethoxyethanol, water/ethanol, water/diethylene glycol monoethyl ether or the like.
  • the oxidation is usually carried out at temperatures between 10° C. and the boiling point of the mixture, preferably at 50° C. to 100° C.
  • catalysts such as metal salts, metal oxides or metal hydroxides, which contain a transition metal, for example copper, cobalt, manganese or iron, as the metal, can be used to accelerate the oxidation reaction.
  • the reaction product is isolated in a customary manner by filtering it off with suction and washing the filtered material retained with water.
  • reaction mixture can be stirred during the oxidation or thereafter with the addition of an emulsifier or dispersing agent in order to achieve optimum pigment properties.
  • This second reaction variant that is to say isolation of a reaction mixture of a thioindigo derivative and the corresponding 3-hydroxy-1-thionaphthene followed by an oxidation, is therefore also particularly suitable for the preparation of thioindigo compounds having pigment properties, such as, for example, tetrachlorothioindigo.
  • a further process variant for the preparation of thioindigo pigments which are particularly suitable for the mass-dyeing of plastics, such as, for example, PVC, polyacrylonitrile, polypropylene, polyethylene or cellulose derivatives, consists in converting a thioindigo derivative, by the addition of sodium dithionite after the oxidation with air is complete, into its leuco compound, which, if appropriate, is isolated, freshly suspended in water with the addition of a sodium hydroxide solution, to which suspension a surface-active agent may be added, and again oxidised with air. In order to coat the pigment with the surface-active agent, an acidification is then carried out, and the pigment is isolated and dried.
  • plastics such as, for example, PVC, polyacrylonitrile, polypropylene, polyethylene or cellulose derivatives
  • Suitable surface-active agents are abietic acid and abietic acid derivatives, colophony and its derivatives, C 13 - to C 18 -paraffindisulphonic acids or the like.
  • the quantity of these materials is 0.1 to 20, preferably 5 to 15% by weight, relative to the pigment.
  • Pigments thus obtained are distinguished by their high colour intensity, very good dispersibility and a high fastness level.
  • Thioindigo compounds which can be obtained by the process according to the invention are used as dyestuffs for the most diverse areas of application and substrates.
  • halogeno-substituted thioindigo derivatives are intense, brilliant pigments having excellent fastness properties, and although the valuable pigment properties of these products can also be achieved by subsequent finishing methods, this new process produces directly pigments of high purity and excellent colouristic pigment properties even directly.
  • the obtainable dyestuffs are also particularly suitable for use as vat dyestuffs for dyeing cotton.
  • the process according to the invention makes it possible to obtain thioindigo compounds having a high degree of purity in a smooth reaction and in high yields.
  • the moist press cake which is composed of a mixture of 4,4',7,7'-tetrachlorothioindigo and 4,7-dichloro-3-hydroxythionaphthene, is then stirred into 310 ml of water and the resulting mixture is made alkaline with 62 g of 50% strength sodium hydroxide solution.
  • the mixture is then cooled down to 60° C., acidified with 76 ml of 35% strength hydrochloric acid, filtered off with suction and the product is washed with water until neutral and dried.
  • 37.7 g (82.4% of theory) of a red-violet powder are obtained. It is a very intense pigment, which on incorporation into stoving lacquers produces a lacquer having very good flow.
  • Example 2 A procedure analogous to the procedure of Example 1 is followed, but after an oxidation with air has been carried out for 6 hours 24 g of sodium dithionite are added directly and the resulting mixture is stirred for one hour at 60° C. The resulting leuco compound of the tetrachlorothioindigo is then filtered off with suction and washed with a little water. The moist press cake is then suspended in 1,000 ml of water to which 62 g of a 50% strength sodium hydroxide solution have been added. 4 g of abietic acid are then added and a further oxidation with air was carried out at 75°-80° C. in the course of about 5 hours. The mixture is then acidified with 94 ml of hydrochloric acid, stirred for 1/2 hour at 70° C., and the product was filtered off with suction, washed until neutral and dried.
  • the moist press cake which is composed of a mixture of 4,4',7,7'-tetrachlorothioindigo and 4,7-dichloro-3-hydroxy-thionaphthene is stirred into 155 ml of water and the resulting mixture is made alkaline with 31 g of 50% strength sodium hydroxide solution. An oxidation is then carried out for 30 minutes at 40°-42° C. by the addition of a solution of 4.3 g potassium permanganate in 130 ml of water. After the oxidation is complete, the mixture is heated to 95°-100° C. during one hour and stirred at this temperature for a further 2 hours.
  • the moist press cake which is 4,4',7,7'-tetrachlorothioindigo is stirred into 180 ml of water which has been made alkaline with 31 g of 50% strength of sodium hydroxide solution, and the resulting mixture is heated to 70° C. After a further 30 minutes' stirring the pH is adjusted to 1 with the aid of 35 ml of 36% strength hydrochloric acid and the mixture is stirred for 60 minutes at 70° C. after the addition of 0.2 g of a commercially available dispersing agent. The product is then filtered off with suction, washed with water until neutral and dried. 18.8 g (82% theory) of a red-violet powder having good pigment properties are obtained.
  • the moist press cake which is 4,7-dichloro-3-hydroxy-1-thionaphthene, is then stirred into 180 of water, which has been made alkaline with 31 g of 50% strength sodium hydroxide solution.
  • 2.1 g of crystalline iron(III) chloride oxidation is carried out for about 8 hours at 80° C. by passing through about 20 liters of air per hour.
  • the product is filtered off hot with suction, washed with hot sodium hydroxide solution and thereafter washed with water until neutral.
  • the moist filter cake is stirred into 800 ml of water/20 ml of 35% strength hydrochloric acid, and the mixture is heated to 70° C. and stirred for 1/2 hour at this temperature after the addition of 0.3 g of a commercially available dispersing agent.
  • the product is then filtered off with suction, washed with water and dried. 17.4 (76% of theory) of a red-violet powder are obtained, which is a very intense pigment having a good fastness level.
  • the dyestuffs of Examples 7-11 were prepared analogously to Examples 1-5 and are pigments having very good properties:

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Indole Compounds (AREA)
US06/535,543 1981-04-29 1983-09-26 Process for the preparation of thioindigo compounds Expired - Lifetime US4555580A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3117055A DE3117055C2 (de) 1981-04-29 1981-04-29 Verfahren zur Herstellung von Tetrachlorthioindigo
DE3117055 1981-04-29

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US (1) US4555580A (de)
JP (1) JPS6024138B2 (de)
CH (1) CH653046A5 (de)
DE (1) DE3117055C2 (de)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19802081A1 (de) * 1998-01-21 1999-07-22 Clariant Gmbh Verfahren zur Herstellung von 4,4'-Dimethyl-6,6'-dichlorthioindigo

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB467447A (en) * 1935-12-21 1937-06-17 Chem Ind Basel Manufacture of indigoid vat-dyestuffs
GB692962A (en) * 1950-03-24 1953-06-17 Ciba Ltd Manufacture of oxythionaphthenes and symmetrical thioindigoid vat dyestuffs

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE241910C (de) * 1907-03-19
GB622962A (en) * 1946-12-19 1949-05-10 Cinema Television Ltd Improvements in or relating to circuits for operating detecting and/or locating devices

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB467447A (en) * 1935-12-21 1937-06-17 Chem Ind Basel Manufacture of indigoid vat-dyestuffs
GB692962A (en) * 1950-03-24 1953-06-17 Ciba Ltd Manufacture of oxythionaphthenes and symmetrical thioindigoid vat dyestuffs

Also Published As

Publication number Publication date
DE3117055A1 (de) 1982-11-18
JPS57182356A (en) 1982-11-10
CH653046A5 (de) 1985-12-13
JPS6024138B2 (ja) 1985-06-11
DE3117055C2 (de) 1985-08-22

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